TW201040023A - Multilayer base film for hydraulic transfer - Google Patents

Abstract

The purpose of the present invention is to provide a multilayer base film for hydraulic transfer having excellent printing aptitude; and a hydraulic transferred film. The solution mean of the present invention are a multilayer base film for hydraulic transfer which includes X layers selected from the following X1 layer to X3 layer, comprises Y layer of soluble polyvinyl alcohol (PY); and a hydraulic transferred film which is made of printing on one surface of said multilayer base film for hydraulic transfer. X1 layer: a layer having soluble polyvinyl alcohol (PX1). However, the saponification degree and polymerization degree of said soluble polyvinyl alcohol (PX1), and the saponification degree and polymerization degree of said soluble polyvinyl alcohol in the said Y layer (PY) satisfy specific relationship. X2 layer: a layer having soluble polyvinyl alcohol (PX2) and inorganic particle with 20 to 20 μ m of average particle diameter. X3 layer: a layer having at least one soluble resin (X3) selected from the group consisting of polysaccharide and acrylic based resin.

Description

[Technical Field] The present invention relates to a multilayer base film and a hydraulic transfer film for water pressure transfer having a layer containing a water-soluble polyvinyl alcohol. [Prior Art] As a method of printing characters or patterns on a structure having a three-dimensional surface or a curved surface having irregularities, there is a method of printing on a water-soluble polyvinyl alcohol film (hereinafter, a polyvinyl alcohol film is also referred to as a PVA film, and also The polyvinyl alcohol of the raw material is a PVA) single-sided transfer film, and the printing surface is floated upward on the water surface, and the printing surface is hydraulically transferred onto the surface of the structure by pressing the structure from above. . However, when the PVA single-layer hydraulic transfer film floats on the water surface, the film swells and swells, and is curled into a printing surface which is less likely to expand, so that the end portion of the water-pressure transfer film cannot be used, and as a result, There is a problem of reduced yield. It is known that, for example, a water composed of a layer of ruthenium microparticles containing a resin having a solubility parameter of 7 to 11 such as a styrene-methyl methacrylate copolymer and a PVA as a binder is disposed on a PVA film. A film for pressure transfer (base film) or a water-pressure transfer sheet to be printed on the film for water-pressure transfer (base film) (Patent Document 1). However, when the hydraulic transfer sheet is used for the transfer, the transfer property to the transferred molded body (transferred body) is good, but the effect of preventing the water surface from being curled is insufficient as will be described later. [Problem to be Solved by the Invention] The present invention is directed to the problem of the above-described prior art, and the present invention is directed to the problem of the prior art described above. The object of the invention is to provide a multilayer base film for water pressure transfer which has good printability and a water pressure transfer film which is less likely to be curled when floating on a water surface. Means of solving problems

The above object can be attained by a multi-layer base film for water pressure transfer having an X layer selected from the following XI layer to the parent 3 layer and a Y layer containing a water-soluble PVA (PY), and the XI layer contains water-soluble a layer of PVA (PXl); however, the degree of saponification and degree of polymerization of the water-soluble PVA (PXl) are respectively set to A mole % and b, and the degree of saponification of the water-soluble PVA (PY) in the Y layer And the degree of polymerization, when set to c mol % and D, respectively, satisfies the following formula (1) to (6), (1) 2 ^ | AC | ^ 20 (2) 0 ^ | BD | ^ 2000 Ο W ( 3) 80^A^99 (4) 500$ 2500 (5) 75^ C ^ 99 (6) 300^ 2500. X2 layer: a layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20/zm. X3 layer: a layer containing at least one water-soluble resin (X3) selected from the group consisting of a polysaccharide and an acrylic resin. 201040023 The multi-layer base film for hydraulic transfer of the present invention is characterized in that the X layer is the XI layer, and when the swelling degree of the XI layer and the Y layer is E (%) and F (%), respectively, the following formula is satisfied. (7)~(9) is better, (7) 0.1^ | EF |^29.5 (8) 0.5^ 20 (9) 0.6 $ FS 30 . In the multilayer base film for water pressure transfer according to the present invention, the X layer is an X2 layer, and the saponification degree and polymerization degree of the water-soluble polyvinyl alcohol (PX2) are respectively referred to as A mole % &amp; B, and the above Y When the degree of saponification and the degree of polymerization of the water-soluble polyvinyl alcohol (PY) in the layer are respectively set to C mol% and 0, it is preferable to satisfy the following formulas (1) to (6), (1) 2 ^ | AC | ^ 20 (2) 0 ^ | BD | ^ 2000 (3) 80 ^ A ^ 99 (4) 500 ^ B ^ 2500 (5) 75$ CS 99 ❹ (6) 300 SDS 2500. Water pressure in the present invention In the multilayer base film, the X layer is an X3 layer, and the water-soluble resin (X3) is cellulose. The multilayer base film for water pressure transfer according to the present invention is such that the X layer is an XI layer or an X3 layer, and the X layer is further In the multilayer base film for water pressure transfer of the present invention, the X layer is disposed on at least one surface of the multilayer base film for hydraulic transfer, and is disposed at 201040023. The film surface roughness (Ra) of the X layer on the surface is preferably 0.1 to 2/zm. The multilayer base film for water pressure transfer of the present invention is the aforementioned water-soluble polyvinyl alcohol. It is preferred that at least one of PX1), water-soluble polyvinyl alcohol (PX2), and water-soluble polyvinyl alcohol (PY) is a blend of two or more kinds of different polyvinyl alcohols. In the base film, it is preferable that the X layer and/or the Y layer contain 0.01 to 3% by mass of a crosslinking agent. Among them, the crosslinking agent is preferably a boron compound. The multilayer base film for water pressure transfer of the present invention, It is preferable that the X layer and/or the Y layer contain 0.1 to 10% by mass of a surfactant. The multilayer base film for hydraulic transfer of the present invention is such that the Y layer is disposed on a multilayer substrate for hydraulic transfer. It is preferable that the surface of at least one of the films is formed by applying a printed base film for water pressure transfer on one surface of the multilayer base film for water pressure transfer. It is preferable that the hydraulic transfer film is printed on the Y layer. The water pressure transfer film of the present invention preferably has a maximum curl length of 0.2 to 8 cm in the width direction measured using a film having a length of 35 cm x a width of 25 cm. The effect of the invention is more than the water pressure transfer of the invention Further, the base film has good printability. Further, since the water pressure transfer film of the present invention is less likely to be curled when floating on the water surface, the yield of the film is high, and the printed surface is not easily deformed. Therefore, the water pressure transfer film of the present invention In particular, the present invention is excellent in performance when it is used as a surface-printing water-pressure transfer film for use in the printing of the curved surface structure 201040023. [Embodiment] The present invention will be described in further detail below. The multilayer base film has an X layer selected from the following XI layer to the parent 3 layer, and a γ layer containing a water-soluble pva (py) layer: a layer containing a water-soluble PVA (PX1); however, The degree of saponification and the degree of polymerization of the water-soluble PVA (PXl) are respectively set to A mole % and B, and the degree of saponification and degree of polymerization of the water-soluble PVA (PY) in the Y layer are respectively set to c mol % and When 〇, the following formula (1)~(6), (1) 2 ^ | AC |^20 (2) 0 ^ | BD | ^ 2000 (3) 80 ^ 99 (4) 500 ^ BS 2500 (5) 75^ C ^ 99 (6) 300 ^ D ^ 2500 . 0 X2 layer: a layer containing water-soluble PVA (PX2) and inorganic particles having an average particle diameter of 2 to 20 μm. X3 layer: a layer containing at least one water-soluble resin (X3) selected from the group consisting of a polysaccharide and an acrylic resin. In the present invention, it is important that the PVA (PX1, ΡΧ2) and PVa (py) used in the X layer and the γ layer are water-soluble. Here, the water solubility is 2 Å &lt;&gt; (the complete melting time in water is 800 seconds or less, preferably 500 seconds or less, more preferably 300 seconds or less, or 30. The complete melting time is 6 sec or less, preferably 500 sec or less, more preferably 300 sec or less. The lower limit of the above 201040023 complete melting time is not particularly limited 'but preferably 1 second or more, more preferably 2 seconds or more. The complete melting time of PVA can be determined by the method described in the examples below. The water solubility of PV A is determined by appropriately selecting the degree of saponification, degree of polymerization, comonomer, etc. In the case where the multilayer base film for hydraulic transfer of the present invention has the XI layer, the saponification degrees of the PVA (PX1) and (PY) are respectively set to A mole % and 〇 mole %, respectively. When the degree of polymerization of the above PVA (PXl) and (PY) is set to B and D, respectively, it is very important to satisfy the following formulas (1) to (6). (1) 2 ^ | AC | ^ 20 (2) 0^ |BD|^ 2000 (3) 80^ A ^ 99 (4}500S BS 2500 (5) 75^ C ^ 99 (6) 300^ 2500. Thus, the multilayer structure of the X layer and the Y layer is set, The layer uses a water-soluble PVA which is different from each other, and further obtains a multilayer base film for water pressure transfer which is excellent in printability by satisfying the above formulas (1) to (6), and obtains water which is less likely to be curled when floating on the water surface. The pressure-transfer film. In the case where the multilayer base film for hydraulic transfer of the present invention has an XI layer, the saponification degree A of the above PVA (PX1) must be 80 to 99 mol%, preferably 85 to 98 mol%. Further, the polymerization degree B must be 500-2500, preferably 700 to 2400. On the other hand, the saponification degree C of the above PVA (PY) must be 75 to 99 mol%, preferably 80 to 97 mol%. Further, the degree of polymerization D must be 300-2500, preferably 400 to 2400. If the degree of chemical conversion of PVA (PX) and (PY) soap 201040023 exceeds a predetermined number, the solubility of PVA to water is lowered, and the film is transferred. On the other hand, if the degree of saponification is less than a predetermined number, the swelling and dissolution are carried out in a short period of time, and there is a problem that the pattern is distorted and there is no adjustment time in the process. When the degree of polymerization of (PXl) and (PY) exceeds a predetermined number, the stretchability at the time of transfer is lowered, and the viscosity is sticky. On the other hand, if the degree of polymerization is less than a predetermined number, the pattern distortion is caused, and the film strength is lowered, and the film is easily cut at the time of printing. Further, the multilayer base film for hydraulic transfer of the present invention has the XI layer. In the case of the above, the saponification degrees A and C of the above PVA (PXl) and (PY) must satisfy the following relationship (1), and the relationship (1 ') is preferably satisfied. (1) 2 ^ IA-CI ^ 20 (1 ′ ) 3 ^ | A-C |^15 . When A-C丨 is less than 2, the curl of the water surface becomes large. Further, when 丨A-C| exceeds 20, the difference in solubility between the layers becomes large, and fine wrinkles due to the difference in film stretching occur during transfer, and wrinkles are likely to remain on the pattern. Further, as will be described later, the Y layer is suitable as a surface to be printed. Therefore, it is more preferable that the saponification degree C of PVA (PY) used in the Y layer is smaller than the saponification degree A of PVA (PX1) used in the X layer. In the case where the multilayer base film for hydraulic transfer of the present invention has the XI layer, the polymerization degrees B and D of the PVA (PX1) and (PY) must satisfy the following relationship (2)' to satisfy the relationship (2'). It is better. (2) |B-D |^2000 (2,) 〇 ^ | B-D | ^ 1500 . When B-D丨 exceeds 2,000, the difference in solubility between layers becomes large, and at the time of transfer -10- 201040023, fine wrinkles due to the difference in film stretching occur, and wrinkles are likely to remain on the pattern. In the case where the multilayer base film for water pressure transfer of the present invention has an X2 layer, 'the saponification degree of the above PVA (PX2) and (PY) is set to A mole% and C mole%, respectively, and the above PVA (PX2) When the degree of polymerization of (PY) is set to B and D, respectively, it is preferable to satisfy the following formulas (1) to (6). (1) 2^ | AC | ^ 20 (2) 0 ^ | BD | ^ 2000 〇(3) 80 ^ 99 (4) 500$ BS 2500 (5) 75^ C ^ 9 9 (6) 300 ^ D ^ 2500. In the case where the multilayer base film for hydraulic transfer of the present invention has the X2 layer, the saponification degree A of the PVA (PX2) used in the X2 layer is preferably 80 to 99 mol%, more preferably 85 to 97 m. %. Further, the degree of polymerization B is preferably from 500 to 2,500, more preferably from 600 to 2,200. On the other hand, in the case where the multilayer base film for hydraulic press transfer of the present invention has the X2 layer, the saponification degree C of the PVA (PY) used in the γ layer is preferably from 75 to 99 mol%, more preferably 80~97 Moer%. Further, the degree of polymerization D is preferably from 300 to 2,500, more preferably from 500 to 2,200 °. Further, in the case where the multilayer base film for hydraulic transfer of the present invention has an X2 layer, the PVA (PX2) and (PY) are The degree of saponification A and C are preferably such that the following relationship (1) is satisfied, and the relationship (1 ') is more preferable. (1) 2^| A-C |^20 -11- 201040023 (1 ′ ) 3 ^ I A-C |^15 . As will be described later, the Y layer is suitable as a surface to be printed. Therefore, the saponification degree C of PVA (PY) which is more preferably used for the Y layer is smaller than the saponification degree A of PVA (PX2) used for the X2 layer. Further, in the case where the multilayer base film for hydraulic transfer of the present invention has a χ2 layer, the polymerization degrees B and D of the PVA (PX2) and (PY) are preferably satisfied by the following relation (2), and the relationship is satisfied. (2 ') is better. (2) |B-D|^ 2000 (2' ) | B-D | ^ 1500 . In the case where the multilayer base film for hydraulic transfer of the present invention has an X3 layer, the saponification degree of the PVA (PY) used for the Y layer is preferably from 75 to 99 mol%, more preferably from 80 to 97 mol%. . Further, the degree of polymerization of PVA (PY) is preferably from 300 to 2,500, more preferably from 400 to 2,400. In the present specification, the degree of saponification of 'PVA (PX, PX2 and PY) is the ratio of the unit actually converted to the unit of the ethylene glycol by the unit obtained by the saponification conversion into the vinyl alcohol unit, which is based on j. Measured by SK 6 7 2 6. Further, the degree of polymerization (Po) is based on the enthalpy measured by JIS K6726, and the PVA is re-distilled and refined, and is then at 30. (The ultimate viscosity [D] (unit: deciliter / g) measured in water is obtained by the following formula: po = ([ V] x l03 / 8.29) (1/0.62) In the present invention It is also preferable that at least one of the PVA (PX1, PX2) and PVA (PY) is a mixture of two or more kinds of heterogeneous PVA. Specific examples include the following: <1> In the case where the multilayer base film for water pressure transfer of the invention has an XI layer or a -12-.201040023 X2 layer, PVA (PX1 or PX2) is a blend of one type of PVA and two or more types of PVA (PY). &lt;2&gt; When the multilayer base film for hydraulic transfer of the present invention has an X1 layer or an X2 layer, PVA (PX1 or PX2) is a blend of two or more different kinds of PVA, PVA (PY) In the case where the multilayer base film for hydraulic transfer of the present invention has an XI layer or an X2 layer, both PVA (PX1 or PX2) and PVA (PY) are two or more kinds of heterogeneous PVA. In the case of the X3 layer, the PVA (PY) is a blend of two or more kinds of heterogeneous PVA. As PVA (PX1, PX2) And / or PVA (PY), blending 2 kinds When the PVA is used, the PVA of a degree of saponification of 90 mol% or more and a degree of polymerization of 1500 or more are mixed in the case of 5 to 30% by mass of the total mass of the pva in the layer, and the strength and transfer of the film are PVA (PX1, PX2, and PY) is a polymerized vinyl ester monomer, and the obtained vinegar-based polymer can be produced by an lane-forming method. Examples thereof include vinyl formate, vinyl acetate, ethyl propyl acrylate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinegar of pivalic acid, and chain acid. B is vinegar, etc., and vinyl acetate is preferred among them. When the vinyl ester monomer is polymerized, it is necessary to copolymerize other monomers which can be copolymerized in the range which does not impair the effect of the invention. The monomer copolymerizable with the ethylene vinegar monomer may, for example, be an olefin having 2 to 30 carbon atoms such as B, C, L butene or isobutylene; acrylic acid and its salt; and C--13-201040023 Methyl ester, ethyl acrylate, n-propyl acrylate, hydrazine propyl acrylate, η-butyl acrylate Acrylates such as i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methacrylic acid and its salts; methyl methacrylate Ethyl methacrylate, η-propyl methacrylate, i-propyl methacrylate, η-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methacrylic acid Methyl acrylate such as 2-ethylhexyl ester, dodecyl methacrylate or octadecyl methacrylate; acrylamide, N-methyl acrylamide, IN-ethyl acrylamide , hydrazine, hydrazine - methacrylamide, diacetone acrylamide, acrylamide dimethylamine and salts thereof, hydrazine-hydroxymethyl acrylamide and derivatives thereof; Methyl acrylamide, hydrazine-methyl methacrylamide, hydrazine-ethyl methacrylamide, methacrylamine dimethylamine and salts thereof, hydrazine-hydroxymethylmethacrylamide and a methacrylamide derivative such as a derivative; methyl vinyl ether, ethyl vinyl ether, η-propyl vinyl ether, i-propyl vinyl ether, - vinyl ethers such as butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; chlorination Halogenated ethylene such as ethylene, vinylidene chloride, fluorinated ethylene or vinylidene fluoride; allyl compound such as propyl acetate or chloropropene; maleic acid and its salt or its ester; itaconic acid and its salt or its vinegar Vinyl decyl compound such as vinyl trimethoxy decane; isopropenyl acetate; dihydroxy butene derivative; ethylene carbonate vinegar; 3,4-diethyl methoxy-1 butyl, 3,4 _ 2 Oxy-1-butene and the like. Further, as a monomer which is preferably copolymerizable as described above, a monomer N-ethyl succinyl-2-indole ketone represented by the following formula (1), N-ethyl succinyl- 2-- 14- 201040023 N-vinylamines such as caprolactam. CH2=CH-N(R1)-C(=0)-R2 (I) (wherein R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a subunit or an alkyl group having 1 to 5 carbon atoms.) In the formula (1), examples of the carbon number 1 to 3 represented by R1 include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group. Ethyl, propyl 3-butyl, isobutyl, t-butyl, pentyl, isopentyl and the like. As the monomer shown, N-vinylformamide, N-ethylene N-methyl-N-vinylformamide, N-methyl-N-vinyl, and N-vinyl are exemplified. -2-pyrrolidone, which can be exemplified as N-; 嗣院嗣, N-ethyl storage group-3-propyl-2-indole oxime, N-2 dimethyl-2-pyrrolidone, N-vinyl- 3,5-dimethyl-etc. As a further preferred copolymerizable monomer, a monomer may be mentioned. The single system containing a sulfonic acid group contains a salt in the molecule, and can be used as long as it can be copolymerized with the vinyl ester. As exemplified, 2-propenylamine-2-methylpropanesulfonic acid, 2-propenylamine-acid, 2-methylpropenylamine-2-methylpropanesulfonic acid, and the g-ethyldisulfonic acid An alkali metal salt such as an allyl group such as allylsulfonic acid or methacrylsulfonic acid. Among these, from the viewpoint of copolymerization with a vinyl ester or stability at the time of saponification, 2-acrylamide, an acid thereof and an alkali metal salt thereof are preferred. Among them, as an alkali metal, Li, etc. R2 represents a hydrogen atom alkyl group, for example, g represented by R2, an isopropyl group, an alkylamine of the above formula (I), acetamide or the like. Ethyl acetyl- 2,5 _ 2 -pyrrolidone contains a sulfonic acid sulfonic acid group or a specific example thereof, a 1-methylpropane sulfonium metal salt; a hydrocarbon sulfonic acid and the time Reactive 2-methylpropanesulfonate; Na, K, • 15-201040023 The copolymerization ratio of the copolymerizable monomers is preferably 15 mol% or less, more preferably ίο mol% or less. . The lower limit 値 is preferably 0. 01 mol% or more, more preferably 0.05 mol% or more. The X2 layer is mainly composed of inorganic particles containing the above ΡνΑ(ρχ2) and an average particle diameter of 2 to 2 〇 //in. In the conventional PVA single-layer hydraulic transfer film, when the film roll is stored at a high temperature or under a lot of humidity, or during a transfer operation, the film is adhered to each other due to moisture absorption or softening, and the roll end of the film is hydrated. It is dissolved, glued, and cut off when it is rolled out. Further, in the hydraulic pressure transfer sheet of the above-mentioned Patent Document 1, in addition to the prevention of insufficient water surface curling effect, the adhesion prevention and the prevention of the cutting effect are insufficient. Further, a PVA-based film having a storage elastic modulus at a temperature of 20 ° C, a dry environment, and a storage elastic modulus at a temperature of 20 ° C and 80% RH of 10 or less is also proposed, which is used for water-pressure transfer. In order to satisfy the above conditions, a proposal for using a film (Patent Document 2) also discloses a method of further adding an inorganic powder by mixing two types of PVA having different degrees of roadization, and using such a PVA film for hydraulic pressure transfer. The film is still expected to fully satisfy the effect of preventing adhesion, preventing cutting, and preventing curling of the water surface. In contrast, the configuration of the X2 layer and the Y layer having the water-soluble PVA (PX2) and the inorganic particles having an average particle diameter of 2 to 20 #m can be understood from the examples described later, and the printing suitability can be obtained. The multilayer base film for water pressure transfer can be obtained by suppressing the occurrence of curl when floating on the water surface and the film does not adhere to each other, and the film is not cut by the end of the roll, and the water is further excellent in peelability. Press-transfer film. The inorganic substance constituting the inorganic particles is not particularly limited as long as it does not adversely affect other physical properties, and examples thereof include antimony compounds such as dioxane-16·201040023 矽, diatomaceous earth, helium balloon, glass beads, and glass bismuth. Inorganic carbonates such as calcium carbonate and magnesium carbonate; inorganic sulfates such as calcium sulfate, barium sulfate, sodium sulfate, potassium sulfate, zinc sulfate, copper sulfate, iron sulfate, magnesium sulfate, and aluminum sulfate; inorganic sulfites such as calcium sulfite Inorganic nitrates such as ammonium nitrate, sodium nitrate, potassium nitrate; inorganic chlorides such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride; sodium phosphate, potassium chromate, talc, clay, kaolin, mica, bentonite, Mongolian Desulphur, gypsum, dawsonite, dolomite, titanium oxide, carbon black, etc. Among them, bismuth compounds, talc, and clay are preferred, and 矽 compounds are preferred. In the X2 layer, the average particle diameter of the inorganic particles must be 2 to 20/z m' 3 to 15; and the am is preferably 4.5 to 12/zm. If the average particle diameter of the inorganic particles is less than 2/zm, the obtained film becomes easy to adhere. On the other hand, when the average particle diameter of the inorganic particles exceeds 20/zm, it is wound into a roll shape, and when the X layer contacts the surface on the opposite side, the convex portion of the inorganic particles is transferred to the surface or printed. Fall off. In addition, the average particle diameter of the inorganic particles in the present specification is a range of the cross section 100#m2 of the layer containing the inorganic particle, and is observed by an electron microscope, and the particle diameter to be observed is 〇.2/zm or more. For the complete particle, the particle size of the particle is determined individually, and the same operation is repeated by changing the observation point. For the observation point of 10 points in total, the particle diameter of the observed particle having a particle diameter of 0.2 μm or more is obtained, and the obtained particle size can be obtained. The particle diameter of each particle at the 10 o'clock point of the observation point was calculated simply on average. Here, the particle diameter of each particle is obtained by obtaining the longest diameter and the shortest diameter to be observed with an accuracy of 0.1 μm, and the two are simply averaged. -17- 201040023 The inorganic particles are preferably contained in the X2 layer in an amount of 〇.:!~8 mass%, more preferably 0_5 to 5% by mass. When the content of the inorganic particles is less than 〇1% by mass, the effect of adding the inorganic particles may not be obtained. On the other hand, when the content of the inorganic particles is more than 8% by mass, the film becomes hard and can be easily cut or rolled. When the X2 layer is brought into contact with the surface of the opposite side in a roll shape, the convex portion of the inorganic particles is transferred to the surface or the printing is peeled off. The content of the 'inorganic particles' was calculated according to the following formula. Content of the inorganic particles (% by mass) = (mass of inorganic particles X in the X2 layer / mass of the X2 layer) X100 Even if the X layer constituting the multilayer base film for hydraulic transfer of the present invention is XI layer or Χ3 layer In this case, the X layer contains the inorganic particles having an average particle diameter of 2 to 20 μm to prevent adhesion of the film, and it is preferable to improve the slidability during processing. Such a pattern is particularly preferable when the surface of the multilayer base film for water pressure transfer is provided with an X layer and a non-printing surface. The inorganic particles are preferably contained in the XI layer or the X3 layer in an amount of 0.5 to 8% by mass. When the content of the inorganic particles is less than 0.5% by mass, the effect of adding the cerium inorganic particles may not be obtained. On the other hand, when the content of the inorganic particles is more than 8% by mass, the film becomes hard and is easily cut, or is wound into a roll so that the XI layer or the X3 layer contacts the surface on the opposite side, and inorganic particles are present. The convex portion is transferred to the surface or the print is peeled off. Here, the content of the inorganic particles is calculated according to the following formula. Content of inorganic particles (% by mass) = (mass of inorganic particles in XI layer or X3 layer / mass of XI layer or X3 layer) xl 〇〇 'In the present invention' by adding the same inorganic particles in the Y layer -18-201040023 The method can be expected to improve the hardness and strength of the film, and improve the printability and the adhesion of the film during transfer. This aspect is particularly good when the Y layer is disposed on the surface and is not printed. It is important that the water-soluble resin (X3) used in the above X3 layer is selected from the group consisting of polysaccharides and acrylic resins. Examples of the polysaccharide include starch, cellulose, and the like. As the starch, natural starch such as corn starch and potato starch; etherified starch, esterified starch, crosslinked starch, grafted starch, burned dextrin, enzyme modified dextrin, a starch, oxidized starch and the like modified starch ; ^ As cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl fiber Metal salts such as hydroxypropylcellulose, nitrocellulose, cationized cellulose, and sodium salts thereof; and examples of the acrylic resin include metal salts such as polyacrylamide, polyacrylic acid, and sodium salts thereof. One type of these resins may be used alone or two or more types may be used in combination. Among these, in order to achieve the object of the present invention, polysaccharides, particularly cellulose, are more preferred. The viscosity of the aqueous solution of the water-soluble resin (X3) is not particularly limited as long as it is suitable for the formation of ruthenium. Specifically, it is preferred that the viscosity of the aqueous solution of 1% by mass is measured by a B-type viscosity meter at 20 ° C of from 1 to 10,000 Pa·s. It is important that the water-soluble resin (X3) used in the above X3 layer is completely dissolved in water at 20 ° C for 2, 000 seconds or less, preferably 500 seconds or less. The lower limit of the above complete melting time is not particularly limited, but is preferably 1 second or longer, more preferably 2 seconds or longer. The complete melting time of the water-soluble resin (X3) can be specifically determined by the method described in the examples below. The water solubility of the water-soluble resin (X3) can be adjusted by appropriately selecting the resin -19-201040023, the degree of denaturation, the degree of polymerization, and the like of the resin used as the raw material. In recent years, as the size of the transfer-receiving body has increased, or the cost of the small-sized parts has been multi-headed, the expansion of the transferable time range from the surface of the water has become a major issue. In the conventional PVA single-layer hydraulic transfer film, since the transferable time range is limited, improvements such as control of PVA molecular structure, change in composition, and mixing of resins having different solubility have been reviewed, but they are not damaged. Within the scope of other physical properties, the extended transferable time range is limited. Further, even in the hydraulic transfer sheet of Patent Document 1, the transfer time range cannot be said to be sufficiently large, except that it is not expected to have a sufficient curl preventing effect. On the other hand, by having the configuration of the X3 layer and the Y layer containing the water-soluble resin (X3), it is also possible to obtain a multilayer base film for water pressure transfer which is excellent in printability, and can be obtained from the examples described later. It was found that the films were not in close contact with each other, and the film was not cut by the end portion of the roll, and the water transfer transfer film which was large in the transferable time from the surface of the water and which was less likely to be curled. The multilayer base film for hydraulic transfer according to the present invention has the X layer selected from the first layer to the X3 and the Y layer containing the water-soluble PVA (PY) as described above. The specific layer structure includes a two-layer structure of an X layer/Y layer, a three-layer structure of an X layer/Y layer/X layer, a three-layer structure of a Y layer/X layer/Y layer, or a multilayer structure of the above. . Further, the multilayer base film for hydraulic transfer of the present invention may be composed only of the X layer and the Y layer. However, other water-soluble layers other than the X layer and the Y layer may be provided within the range not inhibiting the object of the present invention. Floor. In the multilayer base film for water pressure transfer of the present invention, as described later, the Y layer is suitable as a surface on which printing is performed. Therefore, it is preferable that the Y layer is disposed on at least one surface of the multilayer base film for hydraulic transfer. - 201040023 In terms of productivity, the two layers of the χ/γ layer are better. In the multilayer base film for water pressure transfer according to the present invention, it is preferable that the X layer is disposed on at least one surface of the multilayer base film for water pressure transfer. In this case, the film surface roughness (Ra) measured by JIS Β060 1 of the X layer disposed on the surface is preferably 0.1 to 2 #m, more preferably 0.4 to 2/zm. If the film surface roughness (Ra) of the X layer is less than 0.1 m, the obtained film has a tendency to be easily adhered. On the other hand, if the surface roughness (Ra) of the film of the X layer is more than 2 // m, when the X layer is wound into a roll-like contact on the surface of the opposite side, the convex portion of the inorganic particles is transferred to the surface. And there is a flaw in the printing off. The surface roughness of the film of the X layer can be appropriately adjusted, for example, according to the average particle diameter, the amount of addition, and the film forming conditions, elongation conditions, heating and heat treatment conditions of the film to be described later. In the present invention, the XI layer may be composed only of water-soluble PVA (PXl), and other components than PVA (PXl) may be contained as long as the effects of the present invention are not inhibited. The water-soluble PVA (PXl) content in the XI layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. V. In the present invention, the X2 layer may be composed only of water-soluble PVA (PX2) and the above inorganic particles, and may contain PVA (PX2) and other components other than the inorganic fine particles as long as the effects of the present invention are not inhibited. The total content of the water-soluble PVA (PX2) and the inorganic fine particles in the X2 layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. Further, in the present invention, the X3 layer may be composed only of the water-soluble resin (X3), and may contain other components than the water-soluble resin (X3) as long as the effects of the present invention are not inhibited. The content of the water-soluble resin (X3) in the X3 layer is preferably from 50% by mass to more than 70% by mass, more preferably 70% by mass or more, and even more than 9% by mass. Further, in the present invention, the Y layer may be composed only of water-soluble PVA (PY), and may contain other components than PVA (PY) as long as the effects of the present invention are not inhibited. The content of the water-soluble PVA (PY) in the Y layer is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. In the present invention, the X layer and/or the Y layer contain a crosslinking agent, and it is preferable from the viewpoint of improving transferability, further expanding printability, and accommodating transfer time.印刷 In the printing described later, it is preferred to perform printing on the layer containing the crosslinking agent. The content of the crosslinking agent is preferably ~. 〇1 to 3 mass%, more preferably 0_03 to 2.5 mass%, and more preferably ~·〇 3 to 2 mass%. Here, the content of the crosslinking agent is calculated by the following formula. Crosslinker content (% by mass) = (mass of cross-linking agent in layer/mass of layer) X 1 0 0 As a crosslinking agent, as long as it is compatible with PVA (PX dike or ruthenium) or water-soluble resin ( X3) There is no particular limitation on the cross-linking reaction, for example,

Q Boric acid, calcium borate, cobalt borate, zinc borate, aluminum aluminum silicate, ammonium borate, cadmium borate, boron potassium, copper borate, lead borate, nickel borate, barium borate, barium borate, magnesium borate, manganese borate, boric acid Boron compounds such as lithium, borax, arsenite, borosilicate, saponite, yttrium, and borax; Among these, boron compounds are preferred, and boric acid and borax are more preferred. Further, in the present invention, the X layer and/or the Y layer contains a plasticizer, and is also preferable from the viewpoint of the strength of the film or the prevention of cutting. The content of the plasticizer is preferably from 1 to 30% by mass, more preferably from 2 to 25% by mass, and the content of the plasticizer is calculated by the following formula -22-201040023. Plasticizer content (% by mass) = (mass of plasticizer in the layer / mass of layer) x 1 00 As the plasticizer, a polyhydric alcohol is preferred, and examples thereof include ethylene glycol, glycerin, and diglycerin. Propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, etc. may be used in combination of one type or two or more types. Among these, ethylene glycol, glycerin and diglycerin are preferred. The X layer and/or the Y layer contain a surfactant, and are also suitable from the viewpoints of film formability and transfer suitability. The content of the surfactant is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more. Further, the content of the surfactant is preferably 10% by mass or less, more preferably 7% by mass or less, and still more preferably 5% by mass or less. Here, the content of the surfactant is calculated by the following formula. The content of the surfactant (% by mass) = (the mass of the surfactant in the layer / the mass of the layer) x 100. Examples of the type of the surfactant include an anionic interface active agent, a nonionic surfactant, Cationic surfactant, amphoteric surfactant. Examples of the anionic surfactant include a residual acid type such as potassium laurate; a sulfate type such as zinc sulfate; a sulfonic acid type such as dodecylbenzenesulfonic acid or sodium alkylbenzenesulfonate; and a polyoxyethylene laurel. Ethyl ether phosphate monoethanolamine salt, octyl phosphate potassium salt, lauryl phosphate potassium salt, stearyl phosphate potassium salt, octyl ether phosphate potassium salt, sodium lauryl phosphate sodium salt, fourteen Alkyl phosphate sodium salt, dioctyl phosphate sodium salt, trioctyl phosphate sodium salt, -23- 201040023 polyoxyethylene aryl phenyl ether phosphate potassium salt, polyoxyethylene aryl phenyl ether phosphate Ammonium salts, etc. Examples of the nonionic surfactant include an alkyl ether type such as polyoxyethylene fuel oil and polyoxyethylene lauryl ether; an alkylphenyl ether type such as polyoxyethylene octylphenyl ether; and polyoxyethylene. Alkyl ester type such as laurate; alkylamine type such as polyoxyethylene lauryl amino ether: alkylguanamine type such as polyoxyethylene laurylamine; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; oleic acid An alkane guanamine type such as diethanol decylamine; an allyl phenyl ether type such as a polyoxyalkylene allylic phenyl ether or the like. Examples of the cationic surfactant include amines such as laurylamine hydrochloride; quaternary ammonium salts such as lauryl trimethylammonium chloride; and pyridyl salts such as laurylpyridinium chloride compounds. Further, examples of the amphoteric surfactant include N-alkyl-N,N-dimethylbetaine ammonium salts. The surfactant may be used in combination of one type or two or more types. Further, in the X layer and/or the Y layer, poorly soluble particles typified by raw starch and various kinds of starches may be added. By adding these methods, the hardness, strength, printability, and adhesion of the film during transfer can be improved. The inorganic fine particles, the crosslinking agent, the plasticizer, the surfactant, and the like may be used in advance when the X layer and/or the Y layer are produced or when the coating liquid containing the PVA and/or the water-soluble resin (X3) is produced. In the case where the multilayered base film for water pressure transfer of the present invention has an XI layer, when the degree of swelling of the XI layer and the Y layer is E (%) and F (%}, respectively, the following formula (7) - (( 9) is better. -24- 201040023 (7) 0.1^ I EF I ^ 29.5 (8) 0.5^ E ^ 20 (9) 0.6 刍FS 30 The swelling degree E of the aforementioned XI layer is 0.5-20% preferably '0.7 More preferably, the swelling degree F of the Y layer is 〇.6~30%, preferably 〇·8~20%. If the swelling degree of the XI layer and the enamel layer exceeds a predetermined number 则On the other hand, if the degree of swelling is less than a predetermined number, the stretchability is insufficient and the adhesiveness is deteriorated. ^ Further, the above-mentioned Ε and F systems satisfy the following relationship (7). It is better to satisfy the relationship (7'). (7) 0.1^1 EF |^29.5 (7' ) 0.2^| EF | ^ 20 I EF I is less than 0.1, the single layer film will be the same In addition, when Ε and F satisfy the above relational expressions (8) and (9), although | - F 丨 is often maintained at 2 9.5 or less, in order to suppress interlayer swellability The difference is that the curl generated on the water surface is smaller, and Ε-F丨〇 is preferably 20 or less. The degree of swelling of the XI layer and the ruthenium layer is determined by the method described in the examples below, and the water temperature of the transfer tank and the moisture of the film before transfer can be selected. The method for producing the multilayer base film for hydraulic transfer of the present invention is not particularly limited, and a method of laminating the X layer and the ruthenium layer obtained by previously forming a film, and coating the X layer including the film formation may be mentioned. a method of coating a coating liquid of PVA (PY) used in the enamel layer, a coating liquid containing PVA (PX1) used for forming the Y layer and the XI layer, and a PVA (PX2) used for coating the X2 layer. Coating of inorganic particles-25-201040023 A liquid or a method of coating a coating liquid containing a water-soluble resin (X3) used for the X3 layer, a method of pressing together the X layer and the Y layer, etc. Preferably, the coating is performed. A coating liquid containing PVA (PX1) used for forming the Y layer and the XI layer, a coating coating liquid containing PVA (PX2) and inorganic particles used for the X2 layer, or a water-soluble coating layer for coating the X3 layer. Method of coating liquid of resin (X3) As a method of forming a film of X layer or Y layer in advance, for example, using PVA (PX1, PX2 or PY) or water-soluble resin (X3), a solution containing inorganic particles further, if necessary, a cast film forming method, a wet film forming method (a method of discharging into a weak solvent), or a gel system The membrane method (method of extracting and removing the solvent after cooling and gelatinizing the PV A aqueous solution) and the method of the combination, the PVA (PX1, PX2, or PY containing the plasticizer and the required inorganic fine particles or the solvent described later) Or a water-soluble resin (X3} is melted and melted and formed into a film forming method. Among these, a casting film forming method, a solution coating method, and a melt extrusion film forming method are preferred. PVA (PY) used for coating the X layer and the Y layer which have been previously formed into a film

a method of coating a coating liquid of Q, or a coating liquid containing PVA (PX1) used in a Y layer or an XI layer which has been previously formed, or a coating liquid containing PVA (PX2) and inorganic particles used in the X2 layer, PVA is dissolved in a solvent at a concentration of 1 to 40% by mass (more preferably 2 to 20% by mass), and if necessary, inorganic particles or other additives are added, and then, by a usual coating method, for example, gravure roll coating is used. A method of coating by Meyer bar coating, reverse roll coating, air knife coating, spray coating, or the like. The steps and conditions for coating are not particularly limited, but may be mentioned as "coating on a roll or belt" in film formation -26-201040023 of the first layer (layer coated by a coating liquid) and then drying by hot air. A method of drying or solidifying by a well-known means such as hot roll drying or far-infrared drying; once the initial layer is formed, the subsequent step is applied, followed by drying or curing. At this time, it is important to adjust the temperature and amount of the coating liquid, the temperature and timing of drying or curing, and the timing in order not to impair the physical properties of the layer to be formed in advance. As a drying condition, the temperature is 3 Ο ~ 1 2 0. (:, time 3 ~ 200 seconds is preferred. The solvent used as PVA is water, but methanol, ^ ethanol, propanol, dimethyl sulfoxide, dimethylformamide, dimethyl An organic solvent such as acetaminophen or N-methylpyrrolidone. When these organic solvents are used, it is preferably used together with hydrazine. Especially in the case of coating, the drying time can be shortened by mixing methanol, ethanol or propanol. It is preferable to reduce the deterioration of the film before coating. Further, as a method of applying a coating liquid containing a water-soluble resin (X3) used for a Y layer or an X3 layer which has been previously formed, the water-soluble resin (X3) is at a concentration of 1 to 30% by mass is dissolved in a solvent, and a method of coating by gravure roll coating, Meyer bar coating, reverse roll coating, air knife coating, spray coating, or the like is exemplified by a usual coating method. Examples of the solvent of the water-soluble resin (X3) include water, alcohols such as methanol, ethanol, and propanol, and dimethyl hydrazine, a water/alcohol mixture, etc., and the drying time can be shortened. It is preferred to use a water/alcohol mixture. The steps and conditions of coating are In particular, in the film formation of the Y layer, coating of a coating liquid containing a water-soluble resin (X3) on a roll or a belt, followed by hot air drying, hot roll drying, and far-infrared drying are known. The method of drying or solidifying; once the Y layer is formed into a film, the coating liquid containing the water-soluble resin (X3) -27-201040023 is applied in a subsequent step, and then dried or solidified. It is important to damage the physical properties of the γ layer, adjust the temperature and amount of the coating liquid, the temperature and timing of drying or solidification, etc. As a drying condition, the temperature is preferably 3 Ο ~ 1 2 Ot and the time is 3 to 400 seconds. The obtained multilayer film may also be extended by one or two axes before and after the drying step as needed. The extension conditions are a temperature of 2 Ο ~ 1 2 0 ° C, a stretching ratio of 1.05 to 5 times, preferably 1.1 to 3 times. Further, when necessary, the film may be thermally fixed after stretching to reduce the residual stress. When the thickness of the 〇X layer and the Y layer are each a film (when the coating layer is not coated), from the viewpoint of water solubility, each is l〇~ 90//m is better, 15~8〇em is more Good, 20~80# m is better, 20~50/zm is especially good, 25~50//m can also be. When the coating layer is used, the thickness of each is 〇.〇5~20 from m, 0.1 ~1〇/zm is better, 0.1~5/zm is better. Moreover, the thickness of the multilayer base film for hydraulic transfer is preferably 1〇~1〇〇〆m, 20~45; (zm The moisture content of the entire layer of the multilayer film of the X layer, the γ layer, and the water pressure transfer is preferably from 1 to 1% by mass, preferably from 1 to 1% by mass, from the viewpoint of film strength. When the moisture content of the entire layer or the multilayer base film for hydraulic transfer is less than 1% by mass, the layer becomes brittle or the film is easily cleaved. On the other hand, when the water content of the entire layer or the multilayer base film for water pressure transfer exceeds 10% by mass, the film may be stretched during printing to cause the printed pattern to be deviated or the multicolor pattern to fall off. The water content of each layer can be determined by appropriately adjusting the amount of the solvent (water or the like) in the production of the PV layer and the Y layer or the PV A coating liquid, the drying conditions after film formation or coating, and the like. In the multilayer base film for water pressure transfer of the present invention, any of the X layer and the γ layer can be used as a printing surface, but when the X layer is the X1 layer, the layer having a low degree of saponification of the PVA used is used as a printing layer. The surface 'is preferable from the viewpoint of reducing the occurrence of curl as described later and easily washing the transferred printed body, and the γ layer is preferably used as the printing surface. When the X layer is the X2 layer or the X3 layer, it is preferable to use the Y layer as the printing surface from the viewpoint of reducing the occurrence of curl and facilitating the washing of the substrate after transfer. This printing surface is suitable for embossing, and it is preferable to contain a lubricant such as starch or cerium oxide in the layer in advance for the purpose of improving printability and reducing friction with the printing apparatus. Examples of the embossing method include a rubber roller having a general hardness of A10 to 100 (JIS K 6301) and a metal roller having a surface temperature of embossed at a temperature of from 1 to 150 ° C. A processing method in which a multilayer base film for pressure transfer is transferred at a speed of 5 to 50 m/min. Further, when the lubricant is contained, the content of the lubricant is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on the respective layers. Any one of a method of performing embossing and a method of containing a lubricant may be employed, or both may be used. The multilayer base film for hydraulic transfer of the present invention thus obtained can be used as a hydraulic transfer film by performing printing on one surface thereof, for example, in an X layer or a γ layer (preferably a γ layer). The surface is printed as a water pressure transfer film by printing a pattern or a character or the like with a water-insoluble ink or the like. The printed layer of the hydraulic transfer film is floated on the water surface as the upper surface, and the active agent for spraying the ink on the printing surface is required to press the transfer body from above, so that the printed layer is sufficiently fixed on the surface of the transferred body. Then, the X layer and the γ layer are removed by water or the like, dried, and then coated with a protective film such as an acrylic resin to obtain a surface-printed product. Examples of the printing method include gravure printing, screen printing, offset printing, and -29-201040023 roll coating. The printing system can be directly printed on a multilayer substrate film for hydraulic transfer, and once printed on another film, it can be retransferred to a multilayer film for water pressure transfer. The structure to be transferred is a structure having a flat surface and a structure (curved surface) having a curved surface. However, the hydraulic transfer film of the present invention is extremely suitable for transfer of a curved structure. Further, the water-pressure transfer film obtained by using a multilayer base film for water-pressure transfer having three layers is particularly suitable for transfer of a curved structure which is required to have a wide transfer time range. Among them, the curved surface refers to a spherical surface, a undulating surface, a three-dimensional surface having irregularities, and the like. Specific examples of the structure include wood substrates such as wood boards, plywoods, and hard fiberboards; various plastic molded articles; cement products such as pulp cement, slate, glass reinforced concrete, concrete slabs, gypsum board, calcium silicate board, Inorganic products such as magnesium citrate; metal products such as iron, steel, copper, aluminum, alloy, glass products, etc. The water-pressure transfer film of the present invention is excellent in "adhesiveness" in that the film which is softened by water absorption on the water surface is not broken and adheres to the object to be transferred. The adhesion is evaluated by the method described in the examples below, preferably 8 cm or more, more preferably 10 cm or more. Further, the water pressure transfer film of the present invention has a small dimensional change and a small amount of curl when floating on the water surface. Specifically, the maximum curl length (the maximum curl length in the width direction measured by using a film having a length of 35 cm x a width of 25 cm) determined by the method described in the examples below is preferably 0.2 to 8 cm, more preferably 〇. .4~6cm. The loss due to the reduction in the effective area of the transfer is reduced by the method in which the maximum curl length is equal to or less than the above upper limit. Further, by the fact that the maximum curl length is equal to or higher than the above lower limit, the slight curl of the film -30-201040023 floating on the water surface suppresses the expansion of the film end portion, and the printing blur is preferably reduced. The maximum curl length can be adjusted by satisfying the above formula (1), or appropriately selecting the stretching conditions, drying conditions, and the like in the production of the multilayer base film for water pressure transfer. The effective width of the printed pattern is reduced because the hydraulic transfer film is curled, and because the curl causes the printed pattern of the end to be distorted, it actually becomes smaller than the non-curled portion. The effective width of the hydraulic transfer film The width of the film to be used varies depending on the width of the film to be used, and is preferably 60% or more, more preferably 70% or more, according to the method described in the examples described later. The time range is during the period in which the hydraulic transfer film is sufficiently softened and maintains a certain degree of viscosity. The start time of the transfer is when the water pressure transfer film absorbs water on the water surface and is sufficiently softened, usually by pressing. The transfer body can be normally transferred from the bottom to a height of 8 cm as a qualified target. For example, when a film having a thickness of 30 // m is used, the water temperature is usually 30 ° C, 40 seconds before and after. If the water transfer film is made float When the time of the water surface is shorter than the above-mentioned case, the film is insufficient in water absorption, and it tends to become hard and difficult to stretch. As a result, when the object to be transferred is pressed, the film is wrinkled, and the printed pattern is transferred under the folding and deposition, which is easy to be The pattern is wrinkled or twisted. In addition, when the film is pressed against the film, the film is broken, and the pattern on the transfer body is peeled off. On the other hand, if the water pressure transfer film is floated on the water surface, When the time is longer than the above time, the water absorption and dissolution progress, and the viscosity of the film is lowered. Finally, when the pressed body is pressed, the film is broken, and after all, it cannot be transferred. This time limit is -31-201040023, for example, when the film is 30 μm thick. In most cases, the water temperature is 3 (rc, about 2 minutes. Since the water-pressure transfer film of the present invention has a multilayer film of an X layer and a γ layer), it is easier to adjust the solubility than in the case of a single layer film. It does not impair other physical properties. For example, for the Y layer, the P layer (PX1), PVA (PX2), or the X layer containing the water-soluble resin (X3) having a lower solubility than the PVA (PY) constituting the γ layer is laminated. Way, can be substantial The present invention can be specifically described by the following examples, but the present invention is not limited by the examples. Further, the water solubility used in the following examples and comparative examples. The measurement and evaluation methods of the complete dissolution time of the PVA and the water-soluble resin (X3) in water at 20 ° C or 30 ° C, the swelling degree of the X layer and the Y layer, the printability and the transferability are all The following shows: [Measurement method of complete melting time of water-soluble PVA and water-soluble resin (X3) in water at 20 ° C or 30 ° C] 注入Inject 325 ml of ion-exchanged water into a 500 ml glass beaker to keep the water temperature at 2 (TC (30 °C if you want to measure the complete melting time in water at 30 °C). A water-soluble PVA film with a thickness of about 30 m as a sample (to measure the complete melting time of the water-soluble resin (X3), a water-soluble resin (X3) film having a thickness of about 10 μm), at 2 CTC (to be measured) 3 〇 ° C in the water, the complete melting time is 30 ° C), 6 5 % R Η after the temperature adjustment and humidity control 'cut out 3.5 c mx 4 cm size, and clipped in the window frame size of 2.3cmx3_4cm sliding seat, Be fixed. Using an electromagnetic stirrer, the rotor of the glass beaker is stirred at a speed of 28 0 rotation/minute with a rotor of 5 cm in length, and the film sandwiched between the center of the beaker and the sliding seat is quickly impregnated, and Observations ° The film immersed in water passes over the time, dissolves or ruptures on the sliding seat, and detaches from the sliding seat, and gradually dissolves while floating in the water' to become invisible to the naked eye. The time from the impregnation of the film to the invisible to the naked eye, i.e., its complete dissolution time, was measured. [Measurement of Moisture Rate of PVA Layer or Multilayer Film] The moisture content H of the PVA layer or the multilayer film is based on the Vacuum Dryer DP33 manufactured by Yamato Scientific Co., Ltd. and the vacuum pump VR16LP manufactured by Hitachi Machine Co., Ltd. The sample was dried at 50 ° C for 4 hours under reduced pressure of IPa or less, and then the mass M0 before drying of the film and the mass Md after drying were calculated by the following formula. Η (% by mass) = [(MO-Md) / MO] X 1 00 [Method for measuring the degree of swelling of the X layer and the Y layer] In the following examples and comparative examples, the respective preparations were the same as the X layer and the Y layer. A single layer film consisting of 30±3;am is tempered at 20°c, 65%RH, and then cut to a size of 25cm×25cm. After drawing a frame of lOcmxlOcm with an oil-based pen at the center, the oily pen is drawn. As the top, the four sides are not fixed, and the ion-exchanged water floating at 30 °C is measured by the ruler. The length of the square and the horizontal length (L1, L2) of the square drawn by the oily pen after 1 sec. : cm) 'The degree of swelling S is calculated according to the following formula. This measurement was repeated 5 times, and the average was used as the swelling degree of each layer. S(%) = [ {(L1+ L2)/2-10}/10]χΙΟΟ [Printability evaluation method] -33- 201040023 • Pitch deviation For the obtained printed matter, the deviation between the colors is determined based on the following criteria. Very small... The deviation of each color is lower than 〇. 1 mm small... The deviation of each color is O.lmm or more, less than 〇3mm... The deviation of each color is 〇.3mm or more • Printing The off-print was determined for the printed matter obtained, and the print off was determined based on the following criteria. \.) No... There is no 1mm2 or more printing peeling off in 50cmx50cm... There is 1mm2 or more printing off in 50cmx50cm. The number of cuts will be between the printed film and the printed film is 100m, because the film, especially the film end face The number of times the film is cut by the adhesion (the film is cut without considering the mechanical change) is taken as the number of times of cutting. • Printing peeling (adhesiveness) The printed matter (hydraulic transfer film) was placed under a roll and kept at 4 ° C, ^ 80% RH for 1 week. Then, when the film was taken out from the roll, the ink on the printing surface was observed to migrate to the adjacent film surface and peeled off, and it was judged based on the following criteria. No... There is no peeling at all... The area ratio of the peeling part to the whole is less than 5%. The area ratio of the peeling part to the whole is 5% or more, less than 20%. The area ratio of the peeling part to the whole is 20%. The above [transferability evaluation method] -34 - 201040023 - Adhesiveness The obtained printed matter was cut into a circular shape having a diameter of 20 cm and humidity-conditioned at 20 ° C and 65% RH for 24 hours. On the other hand, 35 L of ion-exchanged water (water depth: about 22 cm) was injected into a rectangular parallelepiped having a rectangular shape of 45 cm x 35 cm and a depth of 25 cm, and the film 53 g was dissolved in advance in order to eliminate the influence of PV A eluted during transfer. Adjust to 40 ± 2 °C. As the transfer body, a PET film having a thickness of 50 μm was wound around a cylindrical paper tube having a diameter of 7 cm and a length of 23 cm. The printed circular film was floated in a water tank and waited for 1 minute to make 26 parts by mass of butylated cellulose acetate, 26 parts by mass of butyl carbitol acetate, and 8 parts by mass of butyl methyl propionate polymer. The active agent of the ink composed of a mixture of 20 parts by mass of butyl terephthalate and 20 parts by mass of barium sulfate is sprayed 10 to 15 g per lm 2 film, and the bottom surface of the transfer body is regarded as below, at 20 cm / The sub-speed is submerged into the center of the film for transfer. Observe the film dissolution, cut or print break point and measure the distance from the bottom of the cup to the point. The average measurement was performed 5 times of the same measurement, and the result was used as adhesion. • Maximum curl length ^ From the printed matter adjusted to humidity at 30 ° C and 80% RH, the film forming direction was 43 cm and the width direction was 25 cm (the center of the original film and the center of the cut test piece were identical). A rectangular test piece was prepared, and 1 cm of each end of the short side of the film (edge of 25 cm) was folded into the side of the printing surface to form a slender cylindrical portion, in which an iron rod having a diameter of 2 mm was inserted, and the portion of the film was folded. , fixed with paper tape. On the other hand, in a container of 35 cm x 50 cm x 5.5 cm, the above iron rods 2 can be fixed by a distance of 35 cm, and two pairs of iron rod-embedded depressions are provided at the abyss on the long side of the container. In this container, ion exchange -35- 201040023 water 5L was injected and placed on a hot plate to adjust the water temperature to 30 ± 1 °C. Next, the printed surface of the film was used as the upper surface, and one of the iron bars inserted into the film of the iron bar was inserted into the recess of the container, and the other iron bar was inserted into the other recess to bring the film into contact with the water surface. At this time, it is noted that the film is prevented from biting the bubble and the end of the film is sunk into the water. The film was floated on the surface of the water to cause curling. After 10 seconds, the width of the portion where the central portion of the film was most curled was measured before the film began to swell. The same measurement was carried out 5 times and the average enthalpy was obtained, and the enthalpy was subtracted from the original film width of 25 cm as the maximum crimp length (the maximum curl length in the width direction measured using a film having a length of 35 cm x a width of 25 cm). • Width Effectiveness The same operation as measuring the maximum curl length described above was performed, and the width W (cm) of the substantially untwisted portion of the printed pattern was measured for the film which was floated on the water surface for 20 seconds. The average measurement was performed 5 times of the same measurement, and the width efficiency was calculated by the following formula. Width efficiency (%} = (W/25) xl00 Transferable time (starting time and limit time) Change the time when the film floats in the sink to the transfer time, measure the above adhesion, and set the bottom of the cup to a height of 8 cm. The shortest time during which the wrinkles or the film are broken and the pattern is correctly transferred is the start time of the transfer. On the other hand, the longer the transfer time is, the shorter the adhesiveness is. Therefore, the adhesiveness is 8 cm. [Example 1] The saponification degree was 88% by mol, and the degree of polymerization was 1,700, 20. (: -36-201040023 in water, 15 parts of PVA, completely dissolved for 24 seconds, 15 parts by mass of glycerin, glycerin .65 parts by mass of an aqueous solution (sputum) having a PVA concentration of 15% by mass, cast on a conveyor belt, and subjected to a hot air of 120 ° C on the belt and dried for 5 minutes to obtain a thickness of 30.2 m, a width of 60 cm, and a length. a film of 1050 m (y layer). The film has a moisture content of 3.0% by mass and a glycerin content of 4.0% by mass. Next, a complete solvation degree of 94% by mole of saponification degree, a degree of polymerization of 2000, and 20 °C is completely dissolved. PVA concentration of PVA at a time of 51 seconds The aqueous solution of % was used as a coating liquid (X liquid), and a gravure roll having a gravure width of 54 cm was used, and the film was applied to the film at a rate of 15 m/min, and immediately dried in a hot air of 10 ° C for 30 seconds to obtain a thickness. a multilayer film of a coating layer (X layer) of 1.9/zm. The moisture content of the multilayer film is 3.1% by mass. Further, when a single layer film of the X layer and the Y layer which are separately prepared is used, the degree of swelling is determined by the above method. The swelling degree of the X layer was 8%, and the swelling degree of the Y layer was 21%. The results are shown in Table 1. The two ends of the multilayer film were cut by 5 cm, the width was 50 cm, and the length was After 1000 m, a cylindrical paper tube having an outer diameter of 88.2 mm processed by polyethylene on the surface was continuously wound up under the conditions of a take-up tension of 15 kg/m, a take-up speed of 40 m/min, and a contact roll pressure of 3 kg/m2. Roller for a multilayer base film for hydraulic transfer. A building material ink composed of a mixture of a dye and a barium sulfate of 70% by mass and a mixture of an alkyd resin and a nitrocellulose of 30% by mass is used at 20°. In the environment of C, 6 5% RH, the texture is gravure printed on the above water The Y layer side of the multilayer base film for pressure transfer. The thickness of the printed layer is 2 A m each, the unwinding tension is lkg/m, and the printing speed is 50 m/min. After printing, the multilayer film of -37-201040023 is passed through 60°. The drying zone of lm heated by hot air of C was dried and wound up at a take-up tension of 5 kg/m. The obtained printed matter (hydraulic transfer film) was excellently evaluated by the above method. The results are shown in Table 2. [Example 2] Except that PVA used as a coating liquid (X liquid) was a PVA having a degree of saponification of 96 mol%, a degree of polymerization of 1000 and a complete melting time of water of 20 ° C of 450 seconds, and Example 1 Simultaneously, a multilayer film having a coating layer (X layer) having a thickness of 2.1 μm was obtained. The moisture content of the multilayer film was 3.2% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 5%, and the degree of swelling of the Y layer was 21%. These results are shown in Table 1. Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. [Example 3] A film having a thickness of 32.6/Z m, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 1 except that boric acid was added to the Y solution of Example 1 to have a concentration of 0.15 mass%. Floor). The film had a water content of 3.2% by mass, a glycerin content of 4.0% by mass, and a boric acid content of 0.9% by mass. Next, in the same manner as in Example 1, a multilayer film having a coating layer (X layer) having a thickness of 2.4 wm was obtained. The moisture content of the multilayer film was 3.4% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 8%, and the degree of swelling of the Y layer was -38 to 201040023 12%. The results are shown in Table 1. Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2 » [Example 4] As the coating liquid (X liquid), cerium oxide ("NIPGEL0063" manufactured by Tosoh Corporation) having an average particle diameter of 6.6 / zm was added to the X liquid of Example 1. become

A multilayer film having a coating layer (X layer) having a thickness of 2.8 O was obtained in the same manner as in Example 1 except for 0.4% by mass. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.1% by mass. The moisture content of the multilayer film was 3.2% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 6%, and the degree of swelling of the Y layer was 21%. These results are shown in Table 1. Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. [Example 5] A coating layer having a thickness of 2.6 μm was obtained in the same manner as in Example 3 except that boric acid was added to the X liquid of Example 3 to have a concentration of 0.15% by mass. (X layer) multilayer film. The addition amount (content) of boric acid to the total solid content of the coating liquid (X liquid) was 1.2% by mass. The moisture content of the multilayer film was 3.3% by mass. Further, when the degree of swelling was determined by the above method using a separately formed single layer film of the X layer and the Y layer, the swelling degree of the X layer was 3%, and the swelling degree of the Y layer was 12%. These results are shown in Table 1. -39-201040023 Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. [Comparative Example 1] A film (Y layer) obtained in Example 1 of a single layer was used instead of the multilayer film. In the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the film (Y layer), and various evaluations were provided by the above method. The results are shown in Tables 1 and 2. Ο V / [Comparative Example 2] A film (Y layer) obtained in Example 3 of a single layer was used instead of the multilayer film. In the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the film (Y layer), and various evaluations were provided by the above method. The results are shown in Tables 1 and 2. [Comparative Example 3] Aside from the coating liquid (Y liquid) of Example 1, except that the coating liquid (X liquid) of Example 1 was used, the film (Y layer) of Example 1 was produced in the same manner to obtain a crucible thickness of 31.9/ / m, width 60cm, length 1050m film (Υ layer). The moisture content of the film was 2.9% by mass. Then, in place of the multilayer film, a film (yellow layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from the film (γ layer) in the same manner as in Example 1. The method is provided in various evaluations. The results are not shown in Table 1 and Table 2. [Comparative Example 4] In the same manner as the production of the film (Y layer) in Example 1, except that the aqueous solution (Y liquid) of Example 1 was used instead of the coating of the coating of Example 2, the liquid solution (Y liquid). A film (ruthenium layer) having a thickness of 33.1 mm, a width of 60 cm, and a length of 1050 m was obtained. The moisture content of the film was 3.4% by mass. Next, in place of the multilayer film, a film (yellow layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from the film (Y layer) in the same manner as in Example 1. The method is provided in various evaluations. The results are shown in Tables 1 and 2. [Comparative Example 5] A thickness of 30.7 was obtained in the same manner as in the production of the film (Y layer) of Example 1 except that the aqueous solution (Y liquid) of Example 1 was used instead of the coating liquid (X liquid) of Example 4. Film of /zm, width 60cm, length 1050m (Y layer). The film had a moisture content of 2.9% by mass and a cerium oxide content of 3.1% by mass. Next, in place of the multilayer film, a film (yellow layer) obtained by the above method was used as a single layer, and a printed matter (hydraulic transfer film) was obtained from the film (γ layer) in the same manner as in Example 1. The method is provided in various evaluations. The results are not shown in Table 1 and Table 2. 〇 [Comparative Example 6] In addition to the coating liquid (X liquid), a styrene-methyl methacrylate copolymer (styrene/methyl methacrylate = 50/50, having an average particle diameter of 〇8/zm) was used. Mass ratio) As a dispersing substance, a resin latex having a saponification degree of 88 mol% and a polymerization degree of 1700 pVA as a dispersing agent (concentration of styrene-methyl methacrylate copolymer 1% by mass, saponification degree as a binder 88) A coating layer (X layer) having a thickness of 1.8 &quot; -41 - 201040023 m was obtained in the same manner as in Example 1 except that the molar concentration of the PVA of the polymerization degree of 1750 was 1% by mass and the total solid content concentration was 2% by mass. Multilayer film. The moisture content of the multilayer film was 3.3% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 16%, and the degree of swelling of the Y layer was 21%. The results are shown in Table 1» Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. [Comparative Example 7] Ο In addition to the use of a saponification degree of 70 mol %, a polymerization degree of 1700, 20 ° C in water, a complete melting time of 35 seconds PVA 15 parts by mass, glycerol 0.65 parts by mass of PVA concentration of 15% by mass A film (Y layer) having a thickness of 31.2 / zm, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 1 except for the aqueous solution (Y liquid). The film had a moisture content of 2.8% by mass and a glycerin content of 4.1% by mass. Next, in the same manner as in Example 1, a multilayer film having a coating layer (X layer) having a thickness of 2.2 m was obtained. The moisture content of the multilayer film was 3.0% by mass. Further, when a single-layer film of the X layer and the Y layer which were separately produced was used, and the degree of swelling was determined by the above method, the degree of swelling of the X layer was 8%, and the degree of swelling of the Y layer was 28%. These results are shown in Table 1. Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. [Comparative Example 8] In addition to the use of a saponification degree of 88 mol %, a polymerization degree of 100, a temperature of 100 ° C - 42 - 201040023 in water, a complete melting time of 20 seconds PVA 15 parts by mass, glycerol 0.65 parts by mass PVA concentration 15 A film (Y layer) having a thickness of 25.7/zm, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 1 except for the mass % aqueous solution (Y liquid). The film had a moisture content of 2.7% by mass and a glycerin content of 4.1% by mass. Next, in the same manner as in Example 2, a multilayer film having a coating layer (X layer) having a thickness of 2.4 / zm was obtained. The moisture content of the multilayer film was 3.1% by mass. Further, when a single layer film of the X layer and the Y layer which were separately produced was used, the degree of swelling of the X layer was 5% when the degree of swelling was determined by the above method, and the degree of swelling of the layer of Y was 36%. The results are not shown in Table 1. Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. [Comparative Example 9] In addition to the PVA used in the coating liquid (X liquid), a PVA having a degree of saponification of 94% by mol, a degree of polymerization of 3000, and a complete melting time of water of 20 ° C of 1 〇 5 sec W was used. In the same manner as in Example 1, a multilayer film having a coating layer (X layer) having a thickness of 2.6 was obtained. The moisture content of the multilayer film was 3.5% by mass. Further, when the degree of swelling was determined by the above method using a separately prepared single layer film of the X layer and the Y layer, the degree of swelling of the X layer was 6% ′, and the degree of swelling of the Y layer was 21%. The results are not shown in Table 1. Next, in the same manner as in Example 1, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 2. -43- 201040023

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Φιϋ Ni^ φί^ Tomb s ss table s «stt ωιS cloud ΐ§ ss^ S cloud -13⁄4 201040023 [Example 6] The saponification degree is 88% by mole, and the degree of polymerization is 2000, 30. (: 15 parts by mass of PVA with a complete melting time of 29 seconds in water, 0.65 parts by mass of glycerol, 15% by mass of an aqueous solution (γ liquid) having a PVA concentration of 15% by mass, cast on a conveyor belt, and subjected to hot air at 120 °C The film was dried for 5 minutes to obtain a film (Y layer) having a thickness of 30.4 # m, a width of 60 cm, and a length of 1050 m. The moisture content of the film was 3.1% by mass, and the glycerin content was 4.0% by mass. In the aqueous solution of the same composition, a cerium oxide having a C1 average particle diameter of 6.6/zm ("NIPGEL0063" manufactured by Tosoh Corp.) was added to make a coating liquid (X liquid) of 0.53 mass%, and a gravure width of 54 cm and a depth of 30# were used. A full-mesh gravure roll of m was applied at a speed of 15 m/min, and immediately dried by hot air at 100 ° C for 30 seconds to obtain a multilayer film having a coating layer (X layer) having a thickness of 2.1 / zm. The addition amount (content) of the total solid content of the cerium oxide to the coating liquid (X liquid) was 3.3% by mass. The range of the coating layer (X layer) of the multilayer film was observed by an electron microscope to the range of 〇l〇〇/zm2. , Ο.ΐμπι precision The longest diameter and the shortest diameter of one cerium oxide particle are simply averaged as the particle diameter of the particle. Similarly, the particle diameter of all the particles observed is obtained, and the same operation is repeated by changing the observation point to obtain a total of 10 The particle diameter of all the particles observed in the observation point of the point. When the average particle diameter is calculated by simply averaging the particles having a particle diameter of 0.2/zm or more, it is 6.2/zm. Further, the coating is measured according to JIS B0601. The surface roughness (R a ) of the layer (X layer) was 1.2; / m. Further, the moisture content of the multilayer film was 3.3% by mass. The results are shown in Table-45-201040023 3 ° by a cutting device The two ends of the multilayer film were cut into 5 cm, the width was 50 cm, and the length was l〇〇〇m. The cylindrical paper tube with the outer diameter of 88.2 mm processed by polyethylene on the surface was wound with a tension of 15 kg/m. The film was continuously wound up under the conditions of a speed of 40 m/min and a contact roll pressure of 3 kg/m2 to obtain a roll of a multilayer base film for water pressure transfer. Using a mixture of three colors of dye and barium sulfate, 70% by mass, alkyd resin 30% by mass of a mixture with nitrocellulose The constructed building material was gravure-printed on the Y layer side of the multilayer base film for hydraulic transfer under the environment of 20 ° C and 65% RH. The thickness of the printed layer was 2# m each. The tension was lkg/m, and the printing speed was 50 m/min. After printing, the multilayer film was dried in a drying zone of lm heated by hot air at 60 ° C, and wound up at a take-up tension of 5 kg/m. (Hydraulic transfer film) was excellently evaluated by the above method. The results are shown in Table 4. [Example 7]

In addition to the coating liquid (X liquid), 15 parts by mass of PVA having a complete melting time of 63 seconds in water containing a degree of saponification of 96 mol%, a degree of polymerization of 1700, and 30 ° C, and a PVA concentration of 0.65 parts by mass of glycerin were used. A coating layer having a thickness of 1.9/xm was obtained in the same manner as in Example 6 except that cerium oxide having an average particle diameter of 6.6/zm ("NIPGEL0063" manufactured by Tosoh Corp.) was added in an amount of 0.53 mass%. (X layer) multilayer film. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, the average particle diameter of the cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X-46-201040023 layer) were measured in the same manner as in Example 6 The diameter is 6.0/zm and the surface roughness is 〇_9/zm. Further, the moisture content of the multilayer film was 2.8% by mass. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (7 underpressure transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. [Example 8] In place of the aqueous solution (Y liquid) of Example 6, except that PVA having a degree of saponification of 88 ^ mol%, a degree of polymerization of 2000, and a PVA having a degree of saponification of 96 mol% and a degree of polymerization of 1,700 were used in a mass ratio of 90/ 10 mixed film (complete melting time in water at 30 ° C for 36 seconds) 15 parts by mass, glycerol 0-65 parts by mass of PVA concentration 15% by mass aqueous solution (Y liquid), and film of Example 6 (Y layer) In the same manner, a film (Y layer) having a thickness of 31.lym, a width of 60 cm, and a length of 1050 m was obtained. The film had a moisture content of 2.9% by mass and a glycerin content of 4.3% by mass. Secondly, as a coating liquid (X liquid}, in addition to the use of saponification degree 88 f)

^ Moer %, polymerization degree 17 〇〇, water in 30 ° C, complete dissolution time 24 seconds PVA 15 parts by mass, glycerol 0.65 parts by mass PVA concentration 15% by mass aqueous solution, adding an average particle size of 6.6 ym A multilayer film having a coating layer (X layer) having a thickness of 2.2 # m was obtained in the same manner as in Example 6 except that the cerium oxide ("NIPGEL0063" manufactured by Tosoh Corporation) was 0.53 mass%. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, the average particle diameter of the cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X-47-201040023 layer) were measured in the same manner as in Example 6. The surface roughness is 5.8//m' and the surface roughness is 1.7#m. Further, the moisture content of the multilayer film was 3.3% by mass. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. [Example 9] A film having a thickness of 30, 4 / / m, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 6 except that boric acid was added to the liquid Y of Example 6 to have a concentration of 0.05% by mass. (Y layer). The film had a water content of 2.7% by mass, a glycerin content of 3.8% by mass, and a boric acid content of 0.3% by mass. Next, in addition to the coating liquid (X liquid), PVA 15 parts by mass and glycerin 0.65 parts by mass of PVA having a complete melting time of 51 seconds in a water containing a saponification degree of 94 mol%, a polymerization degree of 2000, and 30 ° C were used. A coating layer having a thickness of 2.4 # m was obtained in the same manner as in Example 6 except that the aqueous solution having a concentration of 15% by mass was added to the cerium oxide having an average particle diameter ("NIPGEL0063" manufactured by Tosoh Corp.) to be 0.53 mass%. Multilayer film of layer X). The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3% by mass. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 6.1 / / m, surface roughness is ll / / m. Further, the moisture content of the multilayer film was 2.8% by mass. These results are shown in Table 3. -48-201040023 Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. [Example 1] In the same manner as in Example 6, except that cerium oxide ("NIPGEL0063" manufactured by Tosoh Corporation) having an average particle diameter of 6.6 μm was added to the liquid Y of Example 6 to have a concentration of 0.3% by mass. A film (Y layer) having a thickness of 30.4 #m, a width of 60 cm, and a length of 1050 m was obtained. The film had a water content of 3.3% by mass, a glycerin content of 4.1% by mass, and a cerium oxide content of 1.9 % by mass. Next, in the same manner as in Example 8, a multilayer film having a coating layer (X layer) having a thickness of 2.0 K/zm was obtained. With respect to the multilayer film, when the average particle diameter of cerium oxide in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 5.7/ / m, surface roughness is 0.7em. Further, the moisture content of the multilayer film was 3.1% by mass. These results are shown in Table 3. Then, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. [Example 1 1] A thickness of 29.1 was obtained in the same manner as in Example 6 except that the polyoxyethylene polyoxypropylene ether as a surfactant was added to the liquid Y of Example 6 to have a concentration of 0.4% by mass. m, a film having a width of 60 cm and a length of 1050 m (Y layer). The film had a moisture content of 3.0% by mass, a C3-49-201040023 alcohol content of 4.0% by mass, and a surfactant content of 2.5% by mass. In the same manner as in Example 6, except that the polyoxyethylene polyoxypropylene ether as a surfactant was added to the X liquid of Example 6 and the concentration was 0.4% by mass. A multilayer film having a coating layer (X layer) having a thickness of 2. m was obtained. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 3.2% by mass, and the amount (content) of the surfactant was 2.4% by mass. With respect to the multilayer film, when the average particle diameter 二 of the ruthenium dioxide and the surface roughness (Ra) of the coating layer (X layer) in the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 6.3. Μιη, surface roughness is 1.5#m. Further, the moisture content of the multilayer film was 3.1% by mass. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. [Example 1 2] In the coating liquid (X liquid), an average particle diameter was added in addition to the substituted cerium oxide.

A multilayer film having a coating layer (X layer) having a thickness of 2.5 &quot; m was obtained in the same manner as in Example 6 except that talc of Q 4.5//m ("P-4" manufactured by Talc Co., Ltd.) was used. The addition amount (content) of the total solid content of the talc to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of the talc in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 4_5/zm. The surface roughness is lO/zm. Further, the moisture content of the multilayer film was 2.9% by mass. These results are shown in Table 3. -50-201040023 Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) obtained from the multilayer film was provided in various evaluations by the above method. The results are shown in Table 4. [Comparative Example 1 〇] A film (Y layer) obtained in Example 6 of a single layer was used instead of the multilayer film. The film was measured to have a surface roughness (r a ) of 0.08 # m in the same manner as in Example 6. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the film (Y layer), and various evaluations were provided by the above method. The results are shown in Table 4. [Comparative Example 1 1] In addition to the coating liquid (X liquid), a styrene-methyl methacrylate copolymer (styrene/methyl methacrylate = 50/50, mass) having an average particle diameter of 0.8/m was used. a resin latex having a saponification degree of 88 mol % and a polymerization degree of 170 0 as a dispersing agent as a dispersing agent. The concentration of the styrene-methyl methacrylate copolymer is 1% by mass, and the degree of saponification as a binder is 8 A multilayer film having a coating layer (X layer) having a thickness of 2.8 m was obtained in the same manner as in Example 6 except that the molar concentration of PVA was 1% by mass and the solid content was 2% by mass. . With respect to this multilayer film, when the surface roughness (Ra) of the coating layer (X layer) was measured in the same manner as in Example 6, it was 2.2 /z m. Further, the moisture content of the multilayer film was 3.2% by mass. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4 -51 - 201040023. [Comparative Example 1 2] A thickness of 29.0 was obtained in the same manner as in the production of the film (layer of ruthenium) of Example 6, except that the coating liquid (X liquid) of Example 6 was used instead of the aqueous solution (sputum) of Example 6. # m, width 60cm, length 1050m film (Υ layer). The film had a moisture content of 2.7% by mass and a glycerin content of 3.9% by mass. Further, in the film, when the average particle diameter and surface roughness (Ra) of cerium oxide were measured in the same manner as in Example 6, the average particle diameter was 6.0 / / m, and the surface roughness was 1 · 〇 #πι. These results are shown in Table 3. Next, in place of the multilayer film, a film (tank layer) obtained by the above method alone was used, and a printed matter (hydraulic transfer film) was obtained from the film (Υ layer) in the same manner as in Example 6, by the above method. Available in various evaluations. The results are shown in Table 4. [Comparative Example 1 3] In addition to the use of a PVA concentration of 15% by mass of a saponification degree of 70 mol%, a degree of polymerization of 1700, a temperature of 1700, 30 ° C, a partial dissolution time of 35 seconds, and a PVA concentration of glycerol 0.65 mass fraction. A film (Y layer) having a thickness of 25. Ο/zm, a width of 6 〇 Cm, and a length of 1050 m was obtained in the same manner as in Example 6 except for the aqueous solution (γ liquid). The film had a moisture content of 3.0% by mass and a glycerin content of 4.3% by mass. In addition to the use of the above-mentioned film as the Y layer, and in the coating liquid (X liquid), a glass powder having an average particle diameter of 21.8 #m ("N powder" manufactured by Nitto Mial Rial) was added instead of cerium oxide, and Examples 6 In the same manner, a multilayer film having a coating layer (X layer) having a thickness of 4.5/zm was obtained. The amount (content) of the total solid content of the glass powder with respect to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of the glass powder in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 21.8//. m, the surface roughness is 23ΑΠ1. Further, the moisture content of the multilayer film was 2.7% by mass. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. [Comparative Example 1 4] A pulverizer of "Super clay" made of Hojun Co., Ltd. was added to the coating liquid (X liquid) instead of cerium oxide (average particle diameter: 1.2/m, measured by HORIBA particle size analyzer LA920) In the same manner as in Example 6, a multilayer film having a coating layer (X layer) having a thickness of 2.8/m was obtained. The addition amount (content) of the total solid content of the bentonite to the coating liquid (X liquid) was 3.3% by mass. With respect to the multilayer film, when the average particle diameter of the bentonite in the coating layer (X layer) and the surface roughness (Ra) of the coating layer (X layer) were measured in the same manner as in Example 6, the average particle diameter was 1.2/im. The surface roughness is 0·07 μm. Further, the moisture content of the multilayer film was 3.2% by mass. These results are shown in Table 3. Next, in the same manner as in Example 6, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 4. -53- 201040023 » » to co eo i- »- 〇&gt; ri w* co cJ ri « 〇4

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Sff: 〆 / 令 令 令 令 令 令 令 令 令 令 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施τ~ m- ^ r-* τ—莩荜军荜荜piur Ttui* v*ij~ 1山|· τα?}* 201040023 Degree 3 Soap 3 , 1 There is a case with a degree of concentration > % ear 15 parts of PVA with a complete melting time of 22 seconds, and an aqueous solution (γ liquid) of propylene glycol 0.65 parts by mass of a PVA concentration of 15% by mass, which were cast on a conveyor belt, and subjected to a hot air of 12 CTC and subjected to 5 After drying for a minute, a film (Y layer) having a thickness of 30.2 #m, a width of 60 cm, and a length of l〇50 m was obtained. The fraction is 3.0% by mass, and the glycerin content is 4.0% by mass. Next, a water-soluble cellulose "CMC (carboxymethyl cellulose) manufactured by DAICEL Chemical Co., Ltd., which has a complete dissolution time of 20 seconds in water at 80 ° C. An aqueous solution having a concentration of 7 mass% of DAICEL 1160 was used as a coating liquid (X liquid). The film was applied to the film at a speed of 15 m/min using a gravure roll having a gravure width of 54 cm, and immediately subjected to a hot air of 10 ° C for 30 seconds. The bell was dried to obtain a multilayer film. When the cross section of the multilayer film was observed under a microscope, the average thickness of the coating layer (X layer) was 2.1 / zm. Further, the surface roughness of the coating layer (X layer) measured according to JIS B0601 ( Ra) was 1.4# m. Further, the moisture content of the multilayer film was 3.0% by mass. The results are shown in Table 5. The both ends of the multilayer film were cut by 5 cm by a cutting device, and the width was After 50cm and a length of 1000m, the cylindrical paper tube with an outer diameter of 88.2mm processed on the surface of the polyethylene was continuously wound up under the conditions of a take-up tension of 15kg/m, a take-up speed of 40m/min, and a contact roll pressure of 3kg/m2. , obtaining a multilayer base film for water pressure transfer a building material ink composed of a mixture of three colors of a mixture of a dye and barium sulfate of 70% by mass and a mixture of an alkyd resin and a nitrocellulose of 30% by mass, in an environment of 20 ° C and 65% RH The texture gravure printing is on the Y layer side of the above-mentioned multilayer base film for water pressure transfer. The thickness of the printed layer was 2; / -56 - .201040023 m, the unwinding tension was lkg/m, and the printing speed was 50 m/min. After printing, the multilayer film was dried in a drying zone of lm heated by hot air at 60 ° C, and taken up at a take-up tension of 5 kg/m. The obtained printed matter (hydraulic transfer film) was subjected to various evaluations by the above method. The results are shown in Table 6. [Example 1 4] In addition to the water-soluble cellulose used in the coating liquid (X liquid), the water-soluble cellulose "METOLOSE6-SH" manufactured by Shin-Etsu Chemical Co., Ltd. was used for 70 seconds in the water at 20 °C. A multilayer film was obtained in the same manner as in Example 13 except that -50" (carboxypropylmethylcellulose, HPMC). When the cross section of the multilayer film was observed under a microscope, the coating layer (X layer) had an average thickness of 1.9 m. Further, the surface roughness (Ra) of the coating layer (X layer) measured in accordance with JIS B0601 was 0.9 μm. Further, the moisture content of the multilayer film was 3.1% by mass. These results are shown in Table 5. Then, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6. [Example 1 5] A film having a thickness of 32.6 # m, a width of 60 cm, and a length of 1050 m was obtained in the same manner as in Example 13 except that boric acid was added to the liquid Y of Example 13 to have a concentration of 0.15% by mass. Floor). The film had a water content of 3.2% by mass, a glycerin content of 4.0% by mass, and a boric acid content of 〇·9% by mass. Next, a multilayer film was obtained in the same manner as in Example 13. When the cross section of the multilayer film was observed under a microscope, the average thickness of the coating layer (X layer) was 2.4 //m. Further, the surface roughness of the coating layer (X layer) measured according to JIS B0601 was -57 - 201040023, and the roughness (Ra) was 1.3 # m. The moisture content of the multilayer film was 3.4% by mass. The results are shown in Table 5. Then, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6. [Example 1 6] In addition to the use of the cerium oxide ("NIPGEL0063" manufactured by Tosoh Corporation) having an average particle diameter of 6.6/zm in the X liquid of Example 13, the concentration was 0.4% by mass. 1 3 Similarly, a multilayer film was obtained. The amount (content) of the total solid content of the cerium oxide relative to the coating liquid (X liquid) was 5.2% by mass. The cross section of the coating layer (X layer) of the multilayer film was observed by an electron microscope to a range of 100/zm 2 , and the longest diameter and the shortest diameter of one cerium oxide particle were determined with an accuracy of 0.1/zm, and the two were simply averaged as the particles. The particle size. Similarly, the particle diameters of all the particles observed were determined, and the observation point was further changed. The same operation was repeated, and the particle diameters of all the particles observed in the observation point of 10 points in total were obtained. In the case where the average particle diameter is calculated by simply averaging the particles having a particle diameter of 0.2 #? or more, it is 6. Ιμιη. Further, when the cross section of the multilayer film was observed under a microscope, the average thickness of the coating layer (X layer) was 3.1 # m, and the surface roughness (Ra) of the coating layer (X layer) measured according to JIS B0601 was 1.5 μm. Further, the moisture content of the multilayer film was 3.2% by mass. These results are shown in Table 5. Then, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6. -58-201040023 [Comparative Example 1 5] A film (Y layer) obtained in Example 13 using a single layer instead of the multilayer film was used. The surface roughness (Ra) of the film measured according to JIS B0601 was O-OSym. These results are shown in Table 5. Then, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the film, and various evaluations were provided by the above method. The results are shown in Table 6. [Comparative Example 1 6] In the same manner as in the production of the film (Y layer) of Example 13, except that the aqueous solution (Y liquid) of Example 13 was used instead of the coating liquid (X liquid) of Example 13 A film (Y layer) having a thickness of 29.4/zm, a width of 60 cm, and a length of 1050 m was obtained. The moisture content of the film was 2.4% by mass. Further, the surface roughness (Ra) of the film measured according to "1860601" was 1.2 m. These results are not shown in Table 5. Then, instead of the multilayer film, a film (Y layer) obtained by the above method was used in a single layer, and a ruthenium printed matter (hydraulic transfer film) was obtained from the film (Y layer) in the same manner as in Example 13. The above methods are provided in various evaluations. The film is easily broken at the time of printing and is difficult to use. Further, even at the time of transfer, it was not sufficiently dissolved in 1 minute, and it was necessary to maintain it for a long time in order to obtain adhesiveness. The results are shown in Table 6. [Comparative Example 1 7] A thickness of 27.8 was obtained in the same manner as in the production of the film (Y layer) of Example 13 except that the aqueous solution (Y liquid) of Example 13 was used instead of the coating liquid (X liquid) of Example 14. Film (γ layer) of /zm, width 60 cm, length 1050 m. The moisture content of the film was 2.8% by mass. Further, the film had a surface roughness (Ra) of 1.4 #m measured according to 31360601 -59 to 201040023. These results are shown in Table 5. Then, in place of the multilayer film, a film (yellow layer) obtained by the above method was used in the same manner as in Example 13, and a printed matter (hydraulic transfer film) was obtained from the film (Y layer). The method is provided in various evaluations. The film is easily broken at the time of printing and is difficult to use. Further, even at the time of transfer, it was not sufficiently dissolved in 1 minute, and it was necessary to maintain it for a long time in order to obtain adhesiveness. The results are not shown in Table 6.比较 [Comparative Example 1 8] A film (Y layer) obtained in Example 15 of a single layer was used instead of the multilayer film. The surface roughness (Ra) of the film measured according to JIS B060 1 was O.l/zm. These results are shown in Table 5. Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the film, and various evaluations were provided by the above method. The results are shown in Table 6. [Comparative Example 1 9] 〇 As the multilayer film, the multilayer film obtained in Comparative Example 6 was used. The surface roughness (R a) of the coating layer (X layer) measured according to JIS B0601 of the multilayer film was 1.3 # m. The results are shown in Table 5. Next, in the same manner as in Example 13, a printed matter (hydraulic transfer film) was obtained from the multilayer film, and various evaluations were provided by the above method. The results are shown in Table 6. -60- 201040023

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Claims (1)

201040023 VII. Patent application scope: 1. A multilayer base film for water pressure transfer, which has an X layer selected from the following XI layer-X3 layer, and a γ layer containing water-soluble polyvinyl alcohol (PY), XI Layer: a layer containing water-soluble polyvinyl alcohol (PX1); however, the degree of saponification and degree of polymerization of the water-soluble polyvinyl alcohol (PX1) are respectively set to A mole % and B, and the water in the Y layer is dissolved. When the degree of saponification and degree of polymerization of the polyvinyl alcohol (PY) are respectively set to c mol% and 0, the following formula is satisfied: (1) {6}, (1) 2^ | AC|^20 〇 (2) 0^ | BD | ^ 2000 (3) 80 ^ A ^ 99 (4) 500 ^ B ^ 2500 (5) 75 ^ C ^ 99 (6) 300S Dg 2500 X2 layer: containing water-soluble polyvinyl alcohol (PX2), And a layer of inorganic particles having an average particle diameter of 2 to 20/zm. X3 layer: a layer containing at least one water-soluble resin (X3) selected from the group consisting of a polysaccharide and an acrylic resin. The multi-layer base film for water pressure transfer according to the first aspect of the invention, wherein the X layer is an XI layer, and the swelling degree of the XI layer and the Y layer is respectively E (%) and F (%). , satisfy the following formula (7 Bu (9), (7) 0.1^ | EF | ^ 29.5 (8) 0.5^ E ^ 20 (9) 0.6 ^ 30. 3. For the multi-layer base film for water pressure transfer according to item 1 of the patent application, wherein - 63- 201040023 The X layer is the X2 layer, and the saponification degree and polymerization degree of the water-soluble polyvinyl alcohol (PX2) are respectively set to Αmol% and 8, and the water-soluble polyvinyl alcohol (PY) in the bismuth layer. When the degree of saponification and the degree of polymerization are respectively set to c mol% and 〇, the following formula is satisfied (1 (6), (1) 2^ | AC|^20 (2) 0^ | BD|^ 2000 ( 3) 80 SAS 99 (4) 500 ^ B ^ 2500 O (5) 75$ CS 99 (6) 300 ^ D ^ 2500. 4. For the multi-layer base film for hydraulic transfer according to item 1 of the patent application, The X layer is the X3 layer, and the water-soluble resin (X3) is cellulose. 5. The multilayer base film for water pressure transfer according to claim 1, 2 or 4, wherein the X layer is XI layer or X3. In the layer, the X layer further contains an inorganic particle having an average particle diameter of 2 to 20/zm, and the multilayered base film for water pressure transfer according to any one of claims 1 to 5, wherein the aforementioned X layer is configured for hydraulic transfer At least one surface of the base film layer, and a thin film disposed on the surface of the X layer of the surface roughness (Ra) of 0.1 ~ 2 μ m. 7. The multilayer base film for water pressure transfer according to any one of claims 1 to 6, wherein the water-soluble polyvinyl alcohol (PX1), water-soluble polyvinyl alcohol (PX2), and water-soluble polyethylene are used. At least one of the alcohols (ργ) is a blend of two or more different kinds of polyvinyl alcohols. 8. The multi-layer base for water pressure transfer according to any one of claims 1 to 7, wherein the X layer and/or the γ layer contains 〇. Agent. 9. The multilayer substrate for water pressure transfer according to item 8 of the patent application scope is a boron compound. 10. The hydraulic transfer base film of any one of claims 1 to 9 wherein the X layer and/or the gamma layer contains a % by weight of a surfactant. The hydraulic pressure-transfer base film according to any one of claims 1 to 10, wherein the Y layer is disposed on at least one surface of the multi-film for hydraulic pressure transfer. A hydraulic transfer film is formed by brushing one surface of a multilayer base film for water pressure transfer according to any one of claims i to 190. The water-pressure transfer film of claim 12, wherein the transfer film is printed on the γ layer. 14. The width measured by a film having a length of 35 cm x a width of 25 cm in the hydraulic transfer film of claim 12 or 13 is a large curl length of 0.2 to 8 cm. -3 mass; in which multi-layer ~ 1 enamel printing is used to apply the water-pressure film to the multi-layer substrate 1 item, the direction of which is -65-201040023. 4. The designated representative figure: (1) The representative figure of the case is: no. (2) A brief description of the symbol of the representative figure: Μ 〇 /η\ V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: